It has long been known that the electrolysis of fluids can result in useful products. Thus, various apparatus and methods have been proposed for electrolyzing saline solution, however, all of the previously available schemes present one or more drawbacks.
For example U.S. Pat. No. 8,323,252 to Alimi et al. teaches a gel formulation for the treatment of diabetic foot ulcer and is incorporated herein by reference in its entirety. Similarly, U.S. Patent Application No. 2012/0164235 to Northey teaches a hydrogel comprising oxidative reductive potential water and is incorporated herein by reference in its entirety.
For example U.S. Pat. No. 7,691,249 teaches a method and apparatus for making electrolyzed water comprising an insulating end cap for a cylindrical electrolysis cell and is incorporated herein by reference in its entirety.
For example, U.S. Pat. Nos. 4,236,992 and 4,316,787 to Themy disclose an electrode, method and apparatus for electrolyzing dilute saline solutions to produce effective amounts of disinfecting agents such as chlorine, ozone and hydroxide ions. Both of these references are incorporated herein by reference in their entireties
U.S. Pat. No. 5,674,537, U.S. Pat. No. 6,117,285 and U.S. Pat. No. 6,007,686 also teach electrolyzed fluids and are now incorporated herein by reference in their entireties.
U.S. Pat. No. 4,810,344 teaches a water electrolyzing apparatus including a plurality of electrolysis devices, each comprising an electrolysis vessel having a cathode and an anode oppose to each other and an electrolysis diaphragm partitioning the space between both of the electrodes wherein the plurality of devices are connected in a series such that only one of the two ionized water discharge channels of the devices constitutes a water supply channel to the device a the succeeding stage and is incorporated herein by reference in its entirety.
U.S. Pat. No. 7,691,249 is now incorporated herein by reference in its entirety and is directed to a method and apparatus for making electrolyzed water.
Methods for treatment of physiological fluids using electrolyzed solutions are set forth in U.S. Pat. No. 5,334,383 which is now incorporated herein by reference in its entirety teaches an electrolyzed saline solution, properly made and administered in vivo, as effective in the treatment of various infections brought on by invading antigens and particularly viral infections.
U.S. Pat. No. 5,507,932 which is now incorporated herein by reference in its entirety teaches an apparatus for electrolyzing fluids.
U.S. Pat. No. 8,062,501 is directed to a method for producing neutral electrolytic water containing OH, O2, HD and HOO as active elements and is incorporated herein by reference in its entirety.
There is a need for stabilized or contained superoxides, hydroxyl radicals and/or OOH* in an aqueous medium, without solvents or catalysts, outside the human body. The art teaches that superoxides, hydroxyl radicals and/or OOH* last for a very short amount of time. Stabilizing superoxides in particular has proven difficult. (Hayyan et al. Generation and stability of superoxide ion in tris(pentafluoroethyl) trifluorophosphate anion-based ionic liquids, Journal of Fluorine Chemistry, Volume 142, October 2012, pages 83-89 and Hayyan et al., Long term stability of superoxide ion in piperidinium, pyrrolidinium and phosphonium cations-based ionic liquids and its utilization in the destruction of chlorobenzenes, Journal of Electroanalytical Chemistry, Volume 664, 1 Jan. 2012, pages 26-32.)
At the time the priority document was filed, superoxides were known to have a very short lifespan. (Kahn et al., SPIN TRAPS: IN VITRO TOXICITY AND STABILITY OF RADICAL ADDUCTS, Free Radical Biology & Medicine, Vol. 34, No. 11, pp. 1473-1481, 2003. AlNashef et al., Electrochemical Generation of Superoxide in Room-Temperature Ionic Liquids. Electrochemical and Solid State Letters, 4 (11) 016-018 (2001). AlNashef et al., Superoxide Electrochemistry in an Ionic Liquid. Ind. Eng. Chem. Res. 2002, 41, 4475-4478. Bielski et al., Reactivity of HO2/O2− Radicals in Aqueous Solution, J. Phys. Chem. Ref. Data, Vol. 14, No. 4 1985. Konaka et al., IRRADIATION OF TITANIUM DIOXIDE GENERATES BOTH SINGLET OXYGEN AND SUPEROXIDE ANION, Free Radical Biology & Medicine, Vol. 27, Nos. 3/4, pp. 294-300, 1999.)
As described in the art, the process of making electrolyzed water requires membranes. (Zhuang et al., Homogeneous blend membrane made from poly(ether sulphone) and poly(vinylpyrrolidone) and its application to water electrolysis, Journal of Membrane Science, Volume 300, Issues 1-2, 15 Aug. 2007, pages 205-210. Sawada et al., Solid polymer electrolyte water electrolysis systems for hydrogen production based on our newly developed membranes, Part I: Analysis of voltage. Progress in Nuclear Energy, Volume 50, Issues 2-6, March-August 2008, pages 443-448. Okada et al., Theory for water management in membranes for polymer electrolyte fuel cells: Part 1. The effect of impurity ions at the anode side on the membrane performances, Journal of Electroanalytical Chemistry, Volume 465, Issue 1, 6 Apr. 1999, pages 1-17. Okada et al. Theory for water management in membranes for polymer electrolyte fuel cells: Part 2. The effect of impurity ions at the cathode side on the membrane performances, Journal of Electroanalytical Chemistry, Volume 465, Issue 1, 6 Apr. 1999, pages 18-29. Okada et al., Ion and water transport characteristics of Nafion membranes as electrolytes, Electrochimica Acta, Volume 43, Issue 24, 21 Aug. 1998, pages 3741-3747. Zoulias et al., (2004), A review on water electrolysis, TCJST, 4(2), 41-71. Xu et al., Ion exchange membranes: state of their development and perspective, Journal of Membrane Science, 263 (2005) 1-29. Kariduraganavar et al., Ion-exchange membranes: preparative methods for electrodialysis and fuel cell applications, Desalination 197 (2006) 225-246. Asawa et al., Material properties of cation exchange membranes for chloralkali electrolysis, water electrolysis, and fuel cells, Journal of Applied Electrochemistry, July 1989, Volume 19, Issue 4, pp 566-570.) Therefore, there is a need for a process to prepare electrolyzed water without a separator or separating membrane/diaphragm.
Reactive oxygen species (ROS) are important in a variety of fields. In medicine there is evidence linking ROS to the aging, disease processes, and the reduction of oxidative stress. Furthermore, ROS are employed as microbicidal agents in the home, hospital and other settings. ROS also include superoxides.
Redox signaling deals with the action of a set of several simple reactive signaling molecules that are mostly produced by mitochondria residing inside cells during the metabolism of sugars. These reactive signaling molecules are categorized into two general groups, Reactive Oxygen Species (ROS), which contain oxidants, and Reduced Species (RS), which contain reductants. These fundamental universal signaling molecules in the body are the simple but extremely important reactive signaling molecules that are formed from combinations of the atoms (Na, Cl, H, O, N) that are readily found in the saline bath that fills the inside of the cells (cytosol). All of the molecular mechanisms inside healthy cells float around in this saline bath and are surrounded by a balanced mixture of such reactive signaling molecules. A few examples of the more than 20 reactive molecules formed from these atoms inside the cell, some of which are discussed herein, are superoxide, hydrogen peroxide, hypochlorous acid and nitric oxide.
Such reactive signaling molecules are chemically broken down by specialized enzymes placed at strategic locations inside the cell. Some of these protective enzymes are classified as antioxidants such as Glutathione Peroxidase and Superoxide Dismutase. In a healthy cell, the mixtures of these reactive signaling molecules are broken down by the antioxidant enzymes at the same rate that they are produced by the mitochondria. As long as this homeostatic balance is maintained, the cell's chemistry is in balance and all is well.
When damage occurs to the cell, for any number of reasons, including bacterial or viral invasion, DNA damage, physical damage or toxins, this homeostatic balance is disturbed and a build-up of oxidants or reductants occurs in the cell. This condition is known as oxidative stress and it acts as a clear signal to the cell that something is wrong. The cell reacts to this signal by producing the enzymes and repair molecules necessary to attempt repairs to the damage and it also can send messengers to activate the immune system to identify and eliminate threats. If oxidative stress persists in the cell for more than a few hours, then the cell's repair attempts are considered unsuccessful and the cell kills and dismantles itself and is replaced by the natural cellular division of healthy neighboring cells.
On a cellular level, this is essentially the healthy tissue maintenance process: damaged cells are detected and repaired or replaced by healthy cells. This cellular repair and regeneration process is constantly taking place, millions of times an hour, in all parts of the body.
There is a need in the art for a safe, effective, economical way of producing superoxides and employing them in the medical industries.